Process for manufacturing aminonaphthol ethers



Patented Dec. 9, 19 30 STATES PA T OFFICE ARTHUR ZITSCHER, OF OFFENBACH-ON-THE-MAIN, GERMANY, ASSIGNOR T GENERAL ANILINE WORKS, IN 0., OF NEW YORK, N. Y., A CORPORATION OF DELAWARE PROCESS FOR MANUFACTURING AlVliILlONAPl-ITI-IOL ETHERS No Drawing. Application filed. December 16, 1927, Serial- No. 240,636, and in Germany January 3, 1927'.

naphtholethercarboxyamides, thus obtained,

10 to the action of alkali metal salts of the by pochlorous or hypobromous acid according to Hofmanns decomposition reaction.

It was by no means to be foreseen that the alkylation of the hydroxynaphthalenecarboXyamides would take place smoothly. It was much more to be expected that a reaction of the alkaline alkylating agent with the carboxyamide. group would take place.

In this manner a series of aminonaphtholethers and their nuclear substitution proclucts is very readily produced which are otherwise obtainable only in a complicated way.

In order to further illustrate my invention the following examples are given, the parts being by Weight and all temperatures in centigrade degrees, but it is to be understood that my invention is not limited to the particular products or reacting conditions mentioned therein.

Emample 1.140 parts of dimethylsulfate and a solution of 187 parts of 2.3-hydroxynaphthoyl-amide in aqueous caustic soda solution are heated to boiling for about 2' hours, while well stirring. After cooling down, the reaction product is filtered, washed and dried.

The 2.3-methoxynaphthoylamide thus, obtained in a good yield, crystallizes from dilute methyl alcohol as fine colorless needles of the melting point 170 (uncon) 201 parts of this 2.3-methoxynaphthoylamide are dissolved in methyl alcohol and mixed in the cold with a solution of hypochlorite of sodium containing 71 parts of free chlorine. To the resulting solution a concentrated caustic soda solution is added and the most of the methyl alcohol is distilled off. The mass is diluted with water and the precipitated, 2.3-aminonaphtholmethylether, thus formed in an excellent yield, is suitably purified by forming the hydrochloride. The

free base of the formula:

crystallizing from dilute alcohol as brilliant colorless lamellas of the melting point 48-49".

Ewample 3.187 parts of 2.6-hydroxynapthoylamide, obtained from 2.6-hydroxynaphthoylchlorioe and ammonia as colorless lamellas of the melting point 209 (uncon), are dissolved incaustic soda solution and heated to boiling with 133 parts of benzylchloride for about 2 hours. The excess of the benzyl-chloride is removed by means of steam and the 2.6-benzylhydroxynaphthoylamide, thus obtained in an excellent yield, is filtered off after cooling. It crystallizes w from dilute acetic acid as colorless needles of a the melting point 198 (uncr.) J By Hofmanns decomposition reaction the 26-aminonaphtholbenzylether of the formula:

' i is formed whichcrystallizes from toluene as colorless lamellas of the melting point 176 '(uncori) "amide, in the form of colorless long spits of 5 the melting point224 (uncor.) whencryst'aL 2.6-eminonaphtholmethylether V crystallizing fromligroine as brilliant needles connected tobunches ofthe meltingpoint 156 157",

In the same way the process maybe carried r outwith other'h droxynaphthoylamides and r their nuclear su stitution products.

In'the following claims the terms alkylating a ent, alkoxygroup and alkyl are inten ed to comprise'w'also .aralkylating agents, aral koxy groups and aralkyl V res ctively. i

claim: r V 1. Process formanufacturi'ng aminonaphtholethers which processcomprises treating hydroxynaphthalenecarboxyamides with -alkylating agents and subjecting the naph-; tholethercarbox amides, thus obtained; to

the actionof al ali metal salts of the hypochlorous orhypobromous acid according to V Hofmanns decomposition reaction. I

2. As new compounds 2.3- aminonaphtholethers oft he formula:

Q 40 a I y a )7 NH 7 O-alkyl wherein the hydrogen atoms of the naphthalene nucleus may be replaced by monovalent substituents, being colorless crystalline products, having definite melting points.

, itholmethylether of theformula i I ,which crystallizes fromligroine in the form of colorless brilliant needles having a melting point ofabout 107 C.

In testimony whereof, I afiix my signature.

ARTHUR ZITSCHER,

In thesamemanner2.6-methoxynaphthoyl-v 1V li'zed" from dilute alcohol, produces the 3. As a new compoundQB-aminonaph- 

